Production of oligomers of 1, 3-dienes



United States Patent PRODUCTEQN GP GLKGGMERS OF lfifilllhES HerbertMueller, Franlrenthal, Pta l, Germany, assignor to Badische AnilindzSoda-l abrili Ahtiengesellsehaft,

Ludwigshaien (Rhine), Germany No Drawing. Filed Dec. 21, 1962, Ser. No.2%,345 Claims priority, application Germany, Mar. 24, 1959,

B 52,534; July 16, 1959, B 54,634; 13, 196%),

13 Claims. (Cl. 269-666) This invention relates to a process for theproduction of oligomers of 1,3-dienes in the presence of a catalyst.More specifically, the invention relates to a process for the productionof oligomers of 1,3-dienes in which a new catalyst system is used. Thepresent application is a continuation-in-part of applications Serial No.15,844, filed March 18,1960, and Serial No. 81,268, filed lanoary 9,1961, both of which o now abandoned and the disclosures of which areincorporated herein by reference as fully as if set forth in theirentirety.

The term oligomers as used in this specification is meant to includeboth opei -chain and cyclic compounds in which the molecules consist ofa small number of 1,3- diene molecules. The oligomers may, for example,contain from 2 to 1,3-diene molecules. The oligomers of 1,3-dienes haveboiling temperatures of up to 150 C. at 10* mm. Hg.

It is known that aluminum alkyls or alkyd-aluminum chlorides andchromium halides or titanium halides can be used for the preparation ofcatalyst syn-terns which convert l,3-dienes into cyclic hydrocarbons,such as cyclododecatriene-(l,5,9) or cyclocctadiene-(1,5). In conersionprocesses of this type, there are also obtained high molecular weight,partly rubberlike, non-distillable polymers. These polymers, While notsoluble, are wellable in the diluents used and turn the reaction mixtureinto a highly viscous mass which is diiiicult to handle and, above all,interferes with continuous operation of the processes.

Another disadvantage of the conventional processe and catalysts residesin the fact that readily flammable and air-sensitive organoaluminurncompounds are required. A furt er disadvantage consists in the fact thatin some cases relatively diiiicultly obtainable chromium halides arenecessary. It is true that the yields are quite good in many cases; justas frequently, however, they are unsa isiactory. The space-time yieldsobtainable by the known methods are also not entirely satisfactory,

It is an object of the present invention to provide a process by whichl,3-dienes can be conver ed into t'L -ir oligomers Without thecompetitive and concurrent formation of appreciable amounts oftroublesome high molecular weight byproducts. Another object of theinvention is to carry out the process with a catalyst system in thepreparation of which organoaluminum compounds and chromium compounds areunnecessary. A fu er object of the invention is to provide a process forthe conversion of 1,3-dienes into their oligomers by which the latterare obtained in better yields and space-time yields than by conventionalmethods.

in accordance with the present invention these and other obiects andadvantages are achieved by carrying out the oligomerization of a1,3-diene with a catalyst system which is obtainable from (a) A ferrichalide or a titanium compound;

(b) At least one metal of Group IA, l r, EB, 111A, 111B, lVA, IVE, VB orVIII? of the Periodic Chart of the Elements, and

(c) At least one halide of an element of Group 113, IIA, IVA or VA ofthe Periodic Chart of the Elements. In this system, either the metal ofgroup (b) must be alu- "ice minum and/ or the halide of group (0) mustbe an aluminum halide, i.e., the presence of aluminum in elementary orcombined form or both is essential.

in many cases, it is advantageous to coernploy with the catalyst systema substance which forms complex compounds with the halides of group (a).Coemplo' merit means adding these complex-forming compounds before,during or after preparing the catalyst system from components (a), (b)and (c).

the new process there are formed cyclic trimers of 1,3-dienes besides asmall amount of cyclic dimers such as cyclooctadiene (1,5) and lvinylcyclohcxene (3). These substances are hereinafter referred to aslower oligomers. Moreover, there are formed higher molecular Weightoligomers of the initial materials, some liquid, some waxy, wlu'chdissolve readily in the common soveuts and which are hereinafterreferred to as higher oligomers. They are higher homologs of cyclictrimers or similar compounds.

The said higher oligomers of 1,3-dienes dissolve in the usual solvents,e.g., benzene, chlorobenzenes, trichloroethylene or cyclohexane, withoutappreciably increasing the viscosity of the reaction mixture.Rubber-like polymcrs are observed in negligible amounts if at all. Forthis reason, the new process is especially suitable for continuousoperation. A further advantage of the process resides in the fact thatby variation of the catalyst components it is possible to otbaiu eitherthe cyclic trimers of the initial material or the said higher oligomerswhich are also important intermediate 1,3 -dienes which are suitable asinitial materials include isoprene, 2,3 dimethylbutadiene (1,3),cyclohexadiene- (1,3) and butadiene-(l,3). The preferred initialmaterials are butadiene-(l,3) and butadiene-(1,3) substituted with oneor two methyl groups. The dienes need not be pure and may be used inadmixture with substances which are inert under the conditions of theprocess. Thus, for example, a gas mixture obtained by dehydrogenation ofbutane or butene may be directly used for the reaction.

Suitable titanium compounds include: titanium(IV) esters of the formulaTHOR), where R is a saturated hydrocarbon radical; titanium halides;titaniurnfi f) ester halides of the formula Ti(OR)X where R is definedas above, X is halogen and :2 an integer from 1 to 3; and alsoorganotitanium halides.

Of the titanium(lV) esters, those are preferred which are derived fromsaturated aliphatic alcohols (preferably ZdliElHOlS) with l to 10,preferably 1 to 4, carbon atoms, or from saturated cycloaliphaticalcohols, preferably 0 cloalkanols with 5 to 10 carbon atoms. Suchesters include titanium tetramethylate, titanium tetraethylate, titaniumtet'apropylate, titanium tetrabutylate, titanium tetraoctylate, titaniumtetracyclohexylate and titanium tetracyclooctylate.

The titanium halides are derived from trivalent or advantageously fromtetravalent titanium. Suitable titanium halides include titaniumflll)chloride, titaniumflll) bromide, titanium(IV) bromide, titanium(lV)fluoride, titanium(1V) iodide and titanium(lV) chloride. Being readilyaccessible, titaniumGV) chloride is the preferred titanium compound forthe production of the catalyst system for the new process.

The preferred titauium(lV) ester halides are derived from the saidhalides, especially from the chlorides, on the one hand, and from theabove-mentioned saturated aliphatic alcohols or saturated cycloaliphaticalcohols on the other hand. Suitable titanium ester halides includediethoxy titanium dichloride, triethoxy titanium monochloride andtricyclohexyloxy titanium monochloride.

Organo-titanium halides may also be used, i.e., compounds in which thereare present, in addition to the halogen, one to three organic radicals,preferably alkyl radicals with 1 to 4 carbon atoms, attached to thetitanium by way of a carbon atom. Examples of such compounds aremethyltitanic trichloride and cyclopentadienyl titanium trichloride.Organo-titanium halides which have united with metal halides to formcomplexes are also suitable titanium compounds for the process accordingto the present invention, for example, C H TiCl .AlCl and C H TiCl.2AlCl Furthermore, it is possible to use iron(I]1) halides, preferablyiron(III) chloride, instead of titanium compounds. Obviously, mixturesof iron(III) halides and titanium compounds can be used.

Of the metals to be used as component (b), lithium, sodium, potassium,beryllium, magnesium, calcium, strontium, barium, boron, aluminum,gallium, indium, thallium, lead, titanium, vanadium, manganese andcerium are preferred. Alloys or mixtures of two or more of the saidmetals may also be used.

Of the halides to be used as component (c), it is preferred to use thechlorides and bromides. Iodides may, however, also be used with goodresults. Suitable com pounds include boron trichloride, aluminumtrichloride, aluminum tribromide, aluminum iodide, galliumtribromide,'indium'tribromide, thallium chloride, carbon tetrachloride,silicon tetrachloride, -tin tetrachloride, zinc chloride, zinc iodide,cadmium chloride and antimony trichloride. Obviously, mixtures of thesehalides may also be used.

If a halogen-containing compound (a) is used and the metal of group (b)is aluminum, then aluminum halide is at least partly formed in situ. Inthis case, addition of a halide (c) is recommended but not essential.

The amounts in which the components(a) titanium compound or iron(III)halide, (b) metal and (c) halide are used in the preparation of thecatalyst may be varied within wide limits. Good results are obtained,for example, with ratios of (a) to (b) to (c) in the range of 1:300:100to 1:10:10. The amounts of (a) and (c) are expressed in moles which, inthe case of the metals (b), the redox equivalents, i.e., the atomicweight divided by the valency, are used, the calculation being based onthe assumption that the metal passes into the most stable oxidationstage.

'The catalyst need only be used in small amounts with reference to the1,3-diene. The reaction proceeds at a satisfactory rate with an amountof, for example, 0.3%

by weight with reference to the 1,3-diene to be reacted. Generallyspeaking, good results are achieved with 0.05 to 5% by weight. largeramount of catalyst.

By adding complex-forming substances, i.e., substances which formcomplex compounds with the halides used, it is possible in many cases topromote the formation of the cyclic trimers of the initial materials atthe expense of the formation of the higher oligomers. The complexformingcompounds are capable of either filling up any electron gaps in thehalide compound or of saturating coordinatively the central atoms of thehalides.

Suitable complex-forming compounds for the purposes of this inventioninclude the salts of alkali and alkaline earth metals, in particulartheir halides, hydrides and salts derived from fatty acids with 1 to 4carbon atoms as well as compounds of oxygen, nitrogen, phosphorus andsulfur containing a single electron pair, such as ethers, thioethers,amines, and organic phosphines. The structure of the organic additivesis not critical. The only requiremerit is that'in addition to' thegroups characteristic of the said classes of substances (O, P: or S)they should either have hydrocarbon structure or contain one or moreadditional atoms and/ or groups which are attached to carbon atoms andwhich are inert under the conditions of the process. Such atoms and Ygroups include halogen atoms attached to an aromatic g, and; &carbonyl,carboxyl, cyano andwarbalkoxy ,4 For practical reasons, those amines,ethers, thioethers and organic phosphines are preferred which inaddition to the group characteristic of the said classes, have onlyhydrocarbon structure and contain up to 20 carbon atoms. The preferredalkali and alkaline earth metal salts are halides, hydrides, cyanides.and salts of lower fatty acids with 1 to 4 carbon atoms. i Primary,secondary and tertiary amines are suitable for use as complex-formingadditives. They may contain aliphatic, cycloaliphatic, araliphaticand/or aromatic radicals. The amino nitrogen atom may also form part ofa heterocyclic ring which may contain one further hetero atom, forexample, oxygen, nitrogen or sulfur.

' Suitable amines include methylamine, dimethylamine, trimethylamine,butylamine, dicyclohexylamine, stearylamine, cyclooctylamine,cyclododecylamine, aniline, N- methylaniline, N,N-dirnethylaniline,naphthylamine, pyridine, quinoline, piperazine, oxazoline, thiazoleandcar bazole.

The ethers, thioethers and organic phosphines which are suitable for useas complex-forming additives may also contain aliphatic, cycloaliphatic,araliphatic and/or aromatic I radicals. The characteristic atom (O, S orP=) may also form part of a heterocyclic ring. Suitable compounds ofthis kind include diethyl ether, diphenyl ether, anisole,p-chloroanisole, glycolic acid methyl ester methyl ether, glycolic acidnitrile methyl ether, dibutyl ether, tetrahydrofuran, dioxane,diphenylene oxide, diethyl sulfide, dibenzyl sulfide,triphenylphosphine, triethylphosphine, thiomorpholine and1,4-dithiacyclohexane.

It is of course also possible to add two or more of the complex-formingadditives at the same time or to use a single compound Which containstwo or more of the said characteristic groups, for example, a compoundwhich is both an amine and a thioether, such as thiomorpholine orphenothiazine.

The complex-forming compounds are advantageously used in such amountsthat the mole ratio of the sum of However, it is also possible to usehalogen compound-l-titanium compound or iron halide to thecomplex-forming compound lies within the limits of 1:01 to 1:3,preferably 120.2 to 1:3. The most favorable ratio can be readilydetermined by a preliminary experiment.

Suitable diluents in the presence of which the process may be carriedout include inert organic solvents such as benzene, toluene, xylene,ethylbenzene, cumene, chlorobenzene, heptane, cyclohexane and isooctane,or a liquid reaction product such as cyclododecatriene-(1,5,9). It isrecommended to use anhydrous and carefully purified solvents. Aromatichydrocarbons With a molecular weight up to 150 are preferred. Solventmixtures may also be used with good results, for example those whichcontain mainly chlorobenzene, heptane or cyclohexane and, in a smalleramount, benzene or toluene. In general, the dilu ent is used in anamount which is about 0.2 to 5 times the amount of 1,3-diene.

The process may be carried out within a wide temperature range, namelybetween about -50 and +150 C. The preferred reaction temperature liesbetween 20 and C.

The process according to this invention is as a rule carried out atatmospheric pressure, but it is also possible to work at reduced orincreased pressure. Increased pressure is often necessary, for'example,up to 10 atmospheres, especially when using low-boiling initialmaterials or diluents and elevated reaction temperatures. The catalystis formed by mixing the components specified. In carrying out theprocess, it is advantageous first to develop the catalyst by intimatelymixing (a) the titanium compound or the iron halide, (b) the metal-forexample in the form of powder, chips or cuttings-and (c) the halide,preferably in the diluent selected for the reaction and in theatmosphere of an inert gas, such as nitrogen or argon, for some time,for example. 10 hours. Mixing may, for example, be carried out in a ballmill or a vibratory mill. The optimum duration of the mixing dependsinter alia on the components used and may be readily ascertained by apreliminary experiment. It should be noted that the activity of thecatalyst may be decreased by mixing for too long a period. The catalystmay also be developed advantageously by mixing only one or two of thecatalyst components, for example the metal and/ or the halogen compoundwith the diluent chosen, the dispersion thus obtained being united witha solution or a dispersion of the titanium compound. Finally, thecatalyst components may be introduced into a solvent and the 1,3-dieneadded immediately with intimate mixing, for example with a highefliciency stirrer.

An especially recommendable method of preparing the catalyst systemcomprises mixing the catalyst components in the presence of an olefine,diolefine, triolefine or tetraolefine or of an acetylene as activator.The terms olefine, diene, triolefine, tetraolefine and acetylene are tobe interpreted in a broad sense. Those compounds are preferred whichhave an unsaturated hydrocarbon structure and contain up to 20 carbonatoms. It is also possible to use compounds with this number of carbonatoms which in addition contain atoms or groups which are inert underthe reaction conditions, i.e., do not, or do not substantially, impairthe course of the reaction. Such atoms or groups include ether bridges,carboxylic ester groups, nitrile groups, carboxylic amide groups, aminoand imino groups, epoxy and sulfide groups.

Suitable olefines include ethylene, isobutene, octadecene-(l),cyclohexene, cyclododecene, styrene, allylbenzene, isopropenylbenzene,ethyl acrylate, ethyl oleate, acrylonitrile, diallyl ether, vinylacetate, allyl methyl sultide, 1,2-epoxy-cyclooctene-(5),N,N-dimethyl-allylamine, N-isopropylacrylamide and methylacrylarnide.

Polyolefines containing 2 to 4 double bonds and acetylene compoundscontaining 1 or 2 carbon triple bonds show a particularly pronouncedactivating effect. Suitable polyenes are for examplecyclooctadiene-(1,S), cyclododecatriene-( 1,5,9)3,3-dimethyl-pentadiene-( 1,4) bicyclo- [2,2, 1 -heptadiene- (2,51-methoxybutadiene-( 1,3 ethyl muconate, cyclooctatetraene,1,2-epoxy-3-methyl-heptadicue-(4,6), divinylacetylene, allene,1,3,5-trivinylcyclohexane and furan. It is particularly advantageous toemploy as activator the 1,3-diene which is to be oligomerized in thesubsequent reaction.

Suitable acetylene compounds are for example: acetylene, vinylacetylene,methylacetylene, dimethylacetylene, phenylacetylene, diphenylacetylene(tolane), ethylpropiolate and octadecyne-(l).

The activator is preferably employed in a molar proportion to thetitanium and/ or iron compound of about 1:1 or higher. It is thuspossible for example to employ a considerable excess of the 1,3-dienewhich is to be oligomerized. The excess is then converted into oligomerswhich act as solvent or diluent. lit a liquid polyene, such ascyclododecatriene-(1,5,9) which cannot be oligomerized, or liquidolefine or acetylene compound, is employed in excess, then this excessacts as diluent. If only a small proportion of activator is employed,e.g., up to moles per mole of titanium and/ or iron compound, or if theactivator is solid, then it is advisable to add an inert diluent asmentioned above. The diluent or the olefinic or acetylenic compound whenused in excess is employed in a proportion of 10 to 100 times the amountof titanium or iron compound.

Activated catalyst systems can be kept for several days withoutsuffering any loss in activity.

The 1,3-dicne is led into the catalyst mixture thus obtained as asuspension whereupon the oligomerization reaction starts withconsiderable evolution of heat. The desired reaction temperature ismaintained by appropriate supply of initial material and if necessary byexternal cooling. To complete the reaction, the temperature ispreferably maintained for some time after the supply of the initialmaterial has ended. Then the catalyst is destroyed, for example, bycareful addition of a small amount of water or an alcohol, such asmethanol or ethanol or by adding a large amount, e.g., 2 to 4'times thequantity of the reaction mixture, of acetone to the reaction mixture,whereby small amounts of polymers are separated. If decomposition of thecatalyst is carried out with alcohol or water, it is recommended firstto add to the mixture a small amount of another substance which containsa single electron pair. Ketones, ethers, ammonia, amines, acid amides,esters and sulfides are for example suitable for this purpose. Themixture is then worked up after decomposition of the catalyst in theusual manner, for example by extraction with water and distillation ofthe organic phase after its separation from the aqueous phase, or, ifdecomposition has been carried out with alcohol or water, bydistillation after separation of the solid components.

The process may also be carried out continuously without difiiculty, forexample, in a tubular coil to which the catalyst suspended in a diluentis supplied continuously at one end and into which the diene is forcedcontinuously and simultaneously at the same end. The reaction mixtureleaving the coiled tube at the other end has methanol added to itcontinuously to decompose the catalyst and the product is then fed to acontinuously operating distillation column.

The hydrocarbons obtainable according to the process are valuableintermediates for organic syntheses. Cyclododecatriene-(1,S,9) can behydrogenated and the resulting cyclodedecene or cyclododecane can beconverted into cyclododecanone oxime which can be rearranged towlaurolactam, a valuable compound for the production of polyamides. Thehigher molecular weight materials, some liquid, some waxy, are forexample suitable for the production of textile auxiliaries and mineraloil auxiliaries or as starting materials for the manufacture of lacquersand plastics. They can also be incorporated in quantities of from 2 to26% by weight into polybutadiene or pclyisoprene to facilitate theincorporation of carbon black prior to vulcanization.

The invention is illustrated by, but not limited to, the followingexamples. The parts are by weight.

EXAMPLE 1 1.l4 parts of titanium tetrachloride, 2 parts of aluminum gritand 3 parts of aluminum chloride are ground for 4 hours in parts ofbenzene in a ball mill. The catalyst suspension thus obtained istransferred under an argon atmosphere into an agitated vessel providedwith a thermometer, a reflux condenser and a gas inlet pipe. Butadieneis led in in a rapid stream while stirring so that the temperaturerapidly rises to 50 C. The reaction temperature is then kept between 50and 60 C. by water cooling. After 30 minutes, 128 parts of butadiene hasbeen absorbed by the catalyst solution. The mix re is stirred foranother 30 minutes and then poured into 320 parts of acetone. 2 parts ofpolybutadiene insoluble in acetone is thus obtained. The acetonesolution is extracted with water and the organic layer dried overcalcium chloride and distilled.

There is obtained 90 parts, i.e., 75% of the theory, ofcyclododecatriene-(1,5,9) with the boiling point 85 C. at a pressure of'7 mm. Hg (n 1.5078) and 7 parts of higher molecular weight butadieneoligomers with the bofling point to C. at a pressure of 10- mm. Hg (111.5160). Elementary analysis, infrared spectrum, hydrogenation iodinenumber and molecular weight show a cyclic hydrocarbon with the empiricalformula (C l-1 h having 6 double bonds per molecule. The distillationresidue is a dark colored oil which has a mean molecular weight of about958 and a hydrogenation iodine number of 390. Elementary analysis givesa carbon content of 88.5% and a hydrogen content of 11.3%, which meansthat the oil consists of butadiene oligomers.

EXAMPLE 3 The procedure of Example 1 is followed but heptane is used asthe solvent. The yield of cyclododecatriene- (1,5,9) is 50% of thetheory and that of high-boiling unsaturated oligomers 8% of the theory.

EXAMPLE 4 A catalyst is prepared in the way described in Example 1 from0.93 part of titanium trichloride, 2 parts of aluminum grit and 3 partsof aluminum chloride in 90 parts of benzene. 75 parts of butadiene isled into the mixture at 65 C. in the course of 2 hours. The mixture isworked up as described in Example 1, 35 parts ofcyclododecadiene-(1,5,9), i.e., 47% of the theory, and 32 parts ofpolyunsaturated higher oligomers, i.e., 43% of the theory, beingobtained. The oligomers for the most part pass over between 100 and 160at 10- mm. Hg.

EXAMPLE 5 -A catalyst is prepared in the way described in Example 1'from 1.14 parts of titanium tetrachloride, 8 parts of aluminum grit and3 parts of aluminum chloride in 90 parts of benzene,.l33 parts ofbutadiene is led into the mixture in the course of 40 minutes Whilecooling. After working up in conventional manner there is obtained 100parts of cyclododecatriene-(1,5,9), i.e., 75% of the theory, and 30parts of polyunsaturated higher oligomers, i.e., 23% of the theory. Lessthan 1% of insoluble polybutadiene is formed.

EXAMPLE 6 A catalyst suspension is prepared from 1.14 parts of titaniumtetrachloride and 2 parts of aluminum grit in 90 parts of benzene bygrinding in a ball mill for 4 hours. 96 parts of butadiene is reacted inthe presence of this catalyst. By working upthe reaction mixture thereare obtained 42 parts of cyclododecatriene-(1,5,9) i.e., 44% of thetheory, and 5 parts of polyunsaturated higher oligomers, i.e., 6% of thetheory.

EXAMPLE 7 1A catalyst is prepared in the way described in Example 1 from1.14 parts of titanium tetrachloride, 2 parts of aluminum grit and 3parts of aluminum chloride in 90 parts of benzene. 60 parts of isopreneis slowly added to the catalyst solution. An exothermic reaction occursthe temperature being kept at50 C. by cooling. When all the isoprene hasbeen added, the mixture is heated for another two hours at 50 C. tocomplete the reaction and then worked up as described in Example 1.There is obtained 36 par-ts of a mixture of isomeric isoprene trimers ofthe boiling point 130 to 150 C. at 7 mm. Hg and with the refractiveindex n 1.5069. 20 parts of a highly viscous oil remains as adistillation residue.

EXAMPLE 8 EXAMPLE 9 A catalyst suspension is prepared inthe waydescribed in Example 1 from 1.14 parts of titanium tetrachloride, 2parts of aluminum grit and 3 parts of aluminum chloride ina mixture of'80 parts of cyclohexane and 10 parts of benzene. Butadiene is led infor 2 hours and after. working up the reaction solution there areobtained 35 parts of cycl0d0decatriene-(1,5,9) and 2 parts of a brownoil. I e

7 EXAMPLE 10 15 parts of aluminum chloride and 15 parts of aluminum gritare ground in 280 parts of benzene for hours in a vibratory mill. 9parts of the suspension formed is added to a solution of 1.4 parts oftitanium chloride in parts of benzene. While stirring vigorously,butadiene is led into the catalyst suspension for half an hour. Byworking up the mixture there are obtained 60 parts ofcyclododecatriene-(1,5,9) and 5 parts of a mobile oil.

EXAMPLE 11 1.14 parts of titanium tetrachloride, 2 parts of aluminumgrit and 90 parts of benzene are ground in a ball mill for 4 hours withan addition of 1 part of iodine for the formation of aluminum iodide.The further procedure of Example 1 is followed, cyclododecatriene-(1,5,9) being obtained in a yieldof of the theory with reference tobutadiene reacted.

EXAMPLE 12 bromine, the yield of cyclod0decatriene-(1,5,9) is 75% of thebutadiene reacted. v

EXAMPLE 13 1.14 parts of titanium tetrachloride, 2 parts of aluminumgrit, 2 parts of aluminum chloride and 6 parts of diphenyl ether inparts of benzene are ground in a The catalyst suspension thus vibratorymill for 4 hours. formed is transferred under an atmosphere of argoninto an agitated vessel fitted with a thermometer, a reflux condenserand a gas inlet pipe. A powerful stream of butadiene is then led inwhile stirring, the mixture heat-L ing up rapidly. The temperature iskept at between50 and 60 C. by cooling with ice-water.

butadiene is absorbed Within 30 minutes. The mixture is stirred foranother 30 minutes and then 10 parts by volume of ether'and 10 parts byvolume of methanol are added. The hydrochloric acid formed byalcoholysis is bound by leading in ammonia. By distilling the mixturethere are obtained parts of cyclododecatriene-(1,5,9),

i.e., 89% of the theory, and about 17 parts of higher molecular weightbutadiene polymers which are however still soluble in acetone and whichremain as a residue together with the residue of the catalyst. Whenworking in the absence of diphenyl ether, the yield ofcyclododecatriene-(l,5,9) is only 75%.

EXAMPLE 14 cyclododecatriene-(1,5,9) is 80% of the theory with referenceto the butadiene used.

EXAMPLE 15 A catalyst is prepared by grinding for three hours in avibratory mill, 2 parts of aluminum grit, 2 parts of alumi-.

num chloride, and 1.14 parts of titanium tetrachloride in 90 parts ofbenzene. chloride is added to the suspension and 131 partsof butadieneis led in Within 40 minutes at 50 C.

The further procedure of Example 13 is followed, 12 6 parts ofcyclododecatriene-(1,5,9) being obtained, i.e., 96% of the theory. As adistillation residue there remain, besides the constituents of thecatalyst, 3 to 5 parts of higher molecular weight products.

168 parts of 2 parts of dry powdered sodium' By proceeding in theabsence of sodium chloride under otherwise identical conditions,cyclododecatriene is obtained in a yield of only 75% of the theory.

By following the procedure of Example 15 but using, instead ofsodiumchloride, other complex-forming com pounds, the results shown inthe following table are obtained.

Table (Examples 16 2'0 24) EXAMPLE 25 A catalyst suspension is preparedas described in Example 15 from 1.14 parts of titanium tetrachloride, 2parts or" aluminum grit, 2 parts of aluminum chloride and 2 parts ofsodium chloride in 8 parts of benzene and 80 parts of heptane. 174 pa tsof butadiene is then led into the mixture at 50 C. in the course of 1.5hours. By Working up in conventional manner there is obtained 120 partsof cyclododecatriene-(1,5,9). This is a yield of 69% of the theory. ByWorking in the absence of sodium chloride, cyclododecatriene is obtainedin a yield of only 50% The procedure of Example 15 is followed, but 56parts of isoprene is used instead of butadiene. The yield of isopreneoligomers is 72% of the theory (boiling point 112 to 145 C. at 8 mm.Hg;n 1.5080).

By Working in the absence of sodium chloride, only 60% of isoprene feedis converted into distillable oligomers.

EXAMPLE 27 The procedure of Example 15 is followed but no aluminumchloride is used in the preparation of the catalyst. The yield ofcyclododecatriene-(1,5,9) is 70% of the theory. By Working in theabsence or" sodium chloride only 44% of the butadiene is converted intocyclododecaniche-(1,5,9).

EXAMPLE 28 A catalyst suspension is prepared as in Example 1 from 90parts of benzene, 2 parts of aluminum grit, 2 parts of aluminum chlorideand 1.14 parts of titanium tetrachloride by grinding for three hours ina vibratory mill. 2.4 parts of diphenyl sulfide is added to the mixtureand butadiene is led in for 30 minutes at 50 to 60 C., 177 parts ofbutadiene being absorbed. The reaction mixture is Worked up inconventional manner. 15 parts, i.e., 85% of the theory, ofcyclododecatriene-(1,5,9) is obtained.

EXAMPLE 29 A catalyst suspension is prepared from 90 parts of benzene, 2parts of aluminum grit, 2 parts of aluminum chloride and 1.14 parts oftitanium tetrachloride as in Example 1 by grinding for three hours in avibratory mill. 0.5 part of diethyl ether is then added to thesuspension and butadiene is led into the mixture at 55 C. for 90minutes. 150 parts of butadiene is reacted. After work ing up thereaction mixture in conventional manner, 122 parts ofcyclododecatriene-(1,5,9) and 20 parts of higher molecular Weightbutadiene oligomers are obtained. The latter are readily soluble inbenzene.

1 0 EXAMPLE 30 A catalyst suspension is prepared as in Example 15 from1.14 parts of titanium tetrachloride, 2 parts of aluminum grit and 2parts of aluminum chloride in parts of benzene. 1.5 parts of powderedsodium acetate is added and butadiene led in for 35 minutes at 50 C. Thereaction mixture is WOliiEd up in conventional manner, 142 parts ofcyclododecatriene-( 1,5,9), i.e., 81% of the theory With reference tothe butadiene reacted, being obtained.

EXAMPLE 31 4.8 parts of iron (Til) chloride, 6 parts of aluminum grit, 6parts of aluminum chloride and 400 parts of henzene are ground for 15hours in a vibratory mill and then 1.5 parts of powdered sodium chlorideis added. The catalyst suspension is saturated with butadiene andstirred for 15 hours at room temperature. The reaction product has 600parts of acetone added to it and the deposited catalyst constituents are1 tered oft. Simultaneously with the inorganic catalyst constituents,about 1 to 2 parts of polybutadiene insoluble in acetone are separated.The acetone solution is Washed With water, dried over calcium chlorideand the mixture is distilled. Distillation yields 30 parts of cyclicbutadiene oligomers composed mainly of an equiinolecular mixture or"trans, trans, transand trans, trans, cis-cyclodedecatriene-(1,5 ,9), asmall amount of an alicyclic hydrocarbon containing a vinyl group andhaving the empirical formula (C l l h, and 15 parts of cyclic butaclienealigomers with a boiling point of 90 to C. at 10* mm. Hg. Elementaryanal sis, molecular Weight and hydrogenation iodine nurnmber show thistraction to be a hydrocarbon with the empirical rormula r sk- 7 parts ofhigher molecular Weight butadiene aligomers remains as a residue.

EXAMPLE 32 A catalyst suspension is prepared by grinding 1.3 parts ofClTi(OC l-l 2 parts of aluminum grit and 4 parts of aluminum chloride in90 parts of benzene in a vibratory mill for three hours. After adding 1part of pulverulent common salt, butadiene is introduced for 30 minutesat 50 C., 123 parts of butadiene being absorbed.

The catalyst is then destroyed by blowing air in and adding somemethanol and the reaction product is distilled. There are obtained 113parts of cyclododecatriene- (1,5,9), i.e., 92% of e theory, and 10 partsof a soft Wax as a residue.

EXAMPLE 3 A catalyst suspension is prepared as described in Example 32from 1.75 parts of titanium tetrabutylate, 2 parts of aluminum grit, 3parts of aluminum chloride, 90 parts of benzene and 0.5 part of sodiumchloride, and 70 parts of butadiene is introduced into the catalystsuspension. After stirring for one hour, the reaction mixture is pouredinto 400 parts of acetone, 8 parts'of polybutadienes which are insolublein acetone being precipitated. From the acetone solution the acetone isremoved by a Water wash. The residual organic phase is dried overcalcium chloride and distilled. There are obtained 39 parts ofcyclododecatrium-(1,5,9) and 10 parts of higher molecular Weightbutadiene oligomers with a boiling point of 120 to C. at a pressure of10- mm. Hg (11 1.509). Elementary analysis, infrared spectrum, molecularWeight and hydrogenation iodine number of these oligomers show abicyclic hydrocarbon with the molecular formula (C H with five doublelinkages. As distillation residue there remains 13 parts of a brown oilwith a molecular Weight of about 1,000, a hydrogenation iodine number of357, a carbon content of 88.5% and a hydrogen content of 11.2%.

EXAMPLE 34 A catalyst suspension is prepared from 100 parts of benzene,2.2 parts of titanium tetrachloride, 2 parts of aluminum grit, 2 partsof aluminum chloride and 0.5 part of pulverulent sodium chloride in themanner described in Example 32. 160 parts of butadiene is reacted in thepresence of this suspension for 40 minutes. The mixture is Worked up asin Example 32, 149 parts of cyclododecatriene-(l,5,9), i.e., 93% of thetheory, and only 10 parts of a distillation residue being obtained.

EXAMPLE 35' A catalyst suspension is prepared from 90 parts of henzene,1.14 parts of titanium tetrachloride, 2 parts of aluminum grit, 2 partsof aluminum chloride and 0.5 part of pulverulent sodium chloride. 48parts of 2,3-dimethylbutadiene-(1,3) is added to this suspension in thecourse of 30 minutes, the reaction temperature being kept at 50 C. Whenall of the 2,3-dimethyl-butadiene-( 1,3) has been added, the mixture isstirred for three hours and then the catalyst is destroyed by addingsome ether and methanol. The reaction product is combined with 400 partsof acetone and filtered 01f from insoluble inorganic catalyst portionswith suction. After the acetone has been removed by a water wash, theorganic phase is evaporated up to a bath temperature of 120 C. at apressure of 5 mm. Hg. 25 parts of a yellow oil remains as a residuewhich according to elementary analysis, molecular weight andhydrogenation iodine number is a hydrocarbon with the empirical formula(C H having four double bonds per molecule.

EXAMPLE 36 The procedure is the same as in Example 35 and 80 parts ofcyclohexadiene-(1,3) is used instead of dimethylbutadiene. Byprecipitation with acetone, 48 parts of a white polymerized product isobtained. The acetone is extracted with water and the organic phase isseparated, dried over calcium chloride and distilled at reducedpressure, 5 parts of dimeric cyclohexadiene being obtained. Analysisshows the hydrocarbon to be a tricyelic compound having two double bondsin the molecule. The compound has a boiling point of 73 to 75 C. at 5mm. Hg (n 1.5316). 24 parts of higher molecular weight viscous oligomersof cyclohexadiene remains as a nondistillable residue.

' EXAMPLE 37 1.14 parts of titanium tetrachloride, 4 parts of zincpowder and 2 parts of aluminum trichloride are ground in 90 parts ofbenzene in a vibratory mill for hours. The catalyst suspension thusformed is transferred under an argon atmosphere to an agitated vesselprovided with a thermometer, reflux condenser and inlet pipe. Butadieneis then led in while stirring. The temperature is kept between50 and 60C. by cooling with Water. 97 parts of butadiene is reacted in the courseof 80 minutes. To complete the reaction, the reaction mixture is stirredfor another hour and then introduced into 500 parts of acetone, 15 partsof high molecular weight polybutadiene being precipitated. The acetonesolution is extracted with water, dried over calcium chloride anddistilled. Distillation gives 65 parts of cyclododecatriene-(1,5,9) and9 parts of viscous oil of molecular weight 450 with the hydrogenationiodine number 170. Elementary analysis and infra-red spectrum show apolycyclic hydrocarbon with three double linkages and the empiricalformula r sh- By working as described above, but using 8 parts ofcadmium instead of zinc and adding as complex-forming agent 1.8 parts ofdiphenyl ether to the catalyst suspension formed, 45 parts ofcyclododecatriene-(1,5,9) and 18 parts of a pale brown oil are obtained.a By working as described above, but replacing the aluminum chloride byan equivalent amount of aluminum bromide or iodide and using 1.8 partsof diphenyl sulfide as complex-forming agent, 90 to 95% of the butadienereacted is converted into cyclododecatriene-(1,5,9).

" Similar yields of cyclododecatriene-(1,5,9) and higher (but stillreadily soluble) butadiene oligomers are obtained byv working asdescribed above, but using as complex-forming substance, 2 parts ofanisol, 2 parts of lithium chloride, 2 parts of potassium iodide, 2parts of magnesium iodide, 2' parts of sodium hydride, 3 parts ofdiphenylene oxide, 2 parts of quinoline, 0.3 part of triphenylphosphineor 05 part of diethyl ether.

EXAMPLE 3 8 A catalyst suspension is prepared as described in Example 1from 1.14 parts of titanium tetrachloride, 2 parts of aluminum granulesand 2 parts of zinc chloride in parts of chlorobenzene and parts ofbutadiene is led in in the course of 15 minutes. Upon working up theproduct, 1 to 2 parts of a mixture of cyclo-octadiene-(LS) andl-vinylcyclohexene-(3), 143 parts of cyclododecatriene-(1,5,9), i.e.,89% of the butadiene reacted, and 18 parts of higher molecular weightbutadiene oligomers readily soluble in benzene are obtained.

By working as described above, but preparing the catalyst from 1 part oftitanium(III) chloride,'2 parts of aluminum, 4 parts of zinc chlorideand 1 part of sodium chloride, there are obtained 100 parts ofbutadiene, 93 parts of cyclododecatriene-(1,5,9) and 6 parts of higherbutadiene oligomers.

By following the procedure of Examples 1 and 2 but using, other catalystsuspensions, the results set out in the table are obtained:

Yield of Example Catalyst suspension prepared from 39 0.4 part ofsodium, 1.14 parts of titani- 30 60 um tetrachloride, 5.0 parts ofaluminum trichloride, 2.0 parts of sodium chloride, 90.0 parts ofbenzene.

1.14 parts of titanium tetrachloride, 58 10 1.0 parts of beryllium, 2.0parts of alluminum trichloride, 90.0 parts of benzene.

1.14 parts of titanium tetrachloride, 45 12 0.2 part of magnesium, 4.0parts of aluminum trichloride, 90.0 parts of benzene.

1.14 parts of titanium tetrachloride, 50 10 0.5 part of calcium, 4.0parts of aluminum trichloride, 90.0 parts of benzene.

1.14 parts of titanium tetrachloride, 85 14 2.0 parts of aluminum, 0.6part of carbon tetrachloride, 0.5 part of sodium chloride, 90.0 parts ofbenzene.

0.57 parts of titanium tetrachloride, 5 55 1.0 parts of gallium, 1.0parts of aluminum trichloride, 0.5 parts of sodium chloride, 90.0 partsof benzene.

1.14 parts of titanium tetrachloride, 32 32 5.0 parts of lead, 2.0 partsof aluminum trichloride, 1.0 parts of sodium chloride, 90.0 parts ofbenzene.

1.14 parts of titanium tetrachloride, 85 8 2.0 parts of aluminum, 1.1parts of tin tetrachloride, 1.0 parts of sodium chloride, 90.0 parts ofbenzene.

1.14 parts of titanium tetrachloride, 86 10 2.0 parts of'aluminum, 2.0parts of antimony trichloride, 90.0 parts of benzene.

1.14 parts of titanium tetrachloride, 81 8 8.0 partsof cerium, 2.0 partsof aluminum chloride, 90.0 parts of benzene.

1.14 parts of titanium tetrachloride, 94 5 4.0 parts of zinc, 3.0. partsof alumiuum bromide, 90.0 parts of ben- Yield of higher Example Catalystsuspension prepared from 53 1.14 parts of titanium tetrachloride, 80

2.0 parts of aluminum, 0.45 parts of silicon tetrachloride, 0.5 parts ofsodium chloride, 90.0 parts of henzone.

1.14 parts of titanium tetrachloride,

8.0 parts of tin, 2.0 parts of aluminum chloride, 90.0 parts of benzene,0.5 parts of sodium chloride.

1.14 parts of titanium tetrachloride, 73

4.0 parts of manganese, 2.0 parts or aluminum chloride, 2.0 parts ofdiphenylene sulfide, 90.0 parts of benzene.

1.14 parts of titanium tetrachloride, 60 35 5.0 parts of an about 50%aluminum] vanadium alloy, 2.0 parts of aluminum chloride, 0.5 parts ofsodium chloride, 90.0 parts of benzene.

2.0 parts of titanium tetra bromide, 40 20 4.0 parts of titanium, 2.0parts of aluminum chloride, 0.5 parts of sodium chloride, 90.0 parts oibenzene.

1.3 parts of Cl2Tl(OC2H5)2, 4.0 parts 70 of zinc, 4.0 parts of aluminumchloride, 1.0 parts of sodium chloride, 90.0 parts of benzene.

1.0 parts of titanium tetrafluoridc, 4.0 83

parts of zinc, 2.0 parts of aluminum chloride, 0.5 parts of sodiumchloride, 90.0 parts of benzene.

EXAMPLE 60 4.8 parts of iron(ll1) chloride, 6 parts of aluminum grit, 6parts of aluminum chloride and 400 parts of henzene are ground for 15hours in a vibratory mill and then 1.5 parts of powdered sodium chlorideare added. The catalyst suspension is then saturated with butadiene andstirred for 15 hours at room temperature. The reaction product has 600parts of acetone added to it. and the deposited catalyst components arefiltered off. About 1 to 2 parts of polybutadiene insoluble in acetoneare separated at the same time with the inorganic catalyst components.The acetone solution is washed with water, dried over calcium chlorideand the mixture distilled. Distillation gives 30 parts of cyclicbutadiene oligomcrs consisting mainly of an equimolecular mixture oftrans,trans,transand trans,trans,cis-cyclododecatriene-(1,5,9) besides asmall amount of an alicyclic hydrocarbon containing vinyl groups andhaving the empirical formula (G l-I 9 and 15 parts of cyclic butadieneoligomers with a boiling point of 90 to 120 C. at 10- mmHg. Elementaryanalysis, molecular Weight and hydrogenation iodine number of thisfraction show a hydrocarbon with the empirical formula (C H 7 parts ofhigher molecular weight butadiene oligomers remains as a non-distillableresidue.

By replacing iron(1]1) chloride by the equivalent amount of iron(lll)bromide, similar yields of cyclododecatriene-(l,5,9) and higherbutadiene oligomers are obtained.

EXAMPLE 61 A catalyst suspension is prepared from 95 parts of toluene,1.14 parts of titanium tetrachloride, 0.05 part of lithium, 0.1 part ofmagnesium, 4 parts of aluminum chloride and 1 part of sodium chloride.115 parts of butadiene is led in in the course of an hour at 50 C. Tocomplete the reaction, the mixture is stirred for another two hours andthen worked up as described in Example 1.

30 parts of trans,trans,cis-cyclododecatriene-(1,5,9) and parts of ahigh molecular weight hydrocarbon are obtained. Molecular weight,elementary analysis, hydrogenation iodine number and infra-red spectrumshow a polycyclic compound with three double linkages in the moleculeand the empirical formula (G l-I 9 i4 EXAMPLE 62 A catalyst suspensionis prepared as described in Example 1 from 1.14 parts of titaniumtetrachloride, 2 parts aluminum grit and 0.6 part of carbontetrachloride. 68 parts of isoprene is added during the course of 15minutes with intense cooling. The reaction temperature is kept between50 and 55 C. After the end of the addition of isoprene, the reactiontemperature is maintained for some time and then the catalyst isdecomposed by adding 6 parts of ether and'6 parts of methanol.

By working up the reaction product, 54 parts of isoprene oligomers withthe boiling point 112 to 150 C. at 8 mm. Hg and a refractive index of 211.5109 is obtained. The yield is 79% with reference to the isopreneintroduced.

EXAMPLE 63 parts of a benzene solution containing about 3 millimoles ofthe complex titanium compound C H TiCl 2AlCl (obtained by refluxingtitanium tetrachloride, aluminum and aluminum chloride in benzene for 8hours) is intimately mixed with 2 parts of zinc and 1 part of aluminumchloride for 3 hours in a vibratory mill.

The catalyst suspension obtained is mixed with 0.2 part of sodiumchloride and saturated with butadiene for 25 minutes. The reactionmixture is then worked up as described in Example 1. 90 parts ofcyclododecatriene- (1,5,9) and 19 parts of waxy butadiene oligomers areobtained.

Similar results are obtained by using, under otherwise identicalconditions 3 millimoles of methyltitanium trichloride orcyclopentadienyltitanium trichloride instead of the above mentionedcomplex titanium compound, and 2 parts of aluminum chloride.

I claim:

1. A process for the production of oligomers of 1,3- dienes whichcomprises adding a 1,3-diene to a catalyst system formed by mixing (a) acompound selected from the class consisting of iron(IH) halides,titanium(1V) acid esters, titanium trihalides, titanium tetrahalides,titanium ester halides and organo-titanium halides; and

(b) metallic aluminum.

2. A process as claimed in claim 1 wherein an aluminum halide isco-employed in the formation of said catalyst system.

3. A process as claimed in claiml wherein a compound capable of formingcomplexes with aluminum halides is co-employed in the formation of saidcatalyst system.

4. A process as claimed in claim 1 wherein an aluminum halide and acompound capable of forming complexes with aluminum halides areco-employed in the formation of said catalyst system.

5. A process as claimed in claim 2 wherein said aluminum halide isformed in situ.

6. A process as claimed in claim 4 wherein said aluminum halide isformed in situ.

7. A process as claimed in claim 1 wherein said 1,3- diene is added tosaid catalyst system and the resulting mixture is maintained at atemperature of 50 to C.

8. A process as claimed in claim 1 wherein said 1,3- diene is added tosaid catalystsystem and reacted to form oligomers in the presence of anaromatic solvent.

9. A process for the production of oligomers of 1,3- diene whichcomprises adding a 1,3-diene to a catalyst system formed by mixing (a) acompound selected from the class consisting of iron(III) halides,titanium(lV) acid esters, titanium trihalides, titanium tetrahalides,titanium ester halides and organo-titanium halides;

15 (b) at least one metal selected from the class consist- 7 ing ofmetals of Groups IA, ]1A, 1113, EA, 1113, IVA, IVB, VB and VIIB of thePeriodic System of the Elements; and (c) at least one halide of anelement selected from the class consisting of the elements of GroupsIIB, 111A, IVA and VA 0f the Periodic System of the Elements;

atleast one ofthe components (12) and (0) being selected from the classconsisting of metallic aluminum and aluminum halide.

10. A process as claimed in claim 9 wherein a halogen-containingcompound (a) and aluminum as metal (b) are used, aluminum halide ashalide (c) being formed in situ.

11. A process as claimed in claim 9 wherein a com- 16 i pound capable offorming complexes with aluminum halides is co-employed.

12. A process as claimed in claim 9 wherein said 1,3- diene is added tosaid catalyst system and the resulting mixture is maintained at atemperature of --50 to '+150 C. i Y 13. A process as claimed in claim 9wherein said 1,3- diene is added to said catalyst system and reacted toform oligomers in the presence of an aromatic solvent.

References Cited in the file of this patent UNITED STATES PATENTS2,504,016 Foster Apr. 11', 1950 2,918,507 Kennedy et al Dec. 22, 19592,964,574 Wilke Dec. 13, 1960 3,076,045 Schneider et a1 I an. 29,1963

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3, 149,174 September 15, 1964 Herbert Mueller I It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 1,, line 70, for "IIA" read IIIA column 10, lines 30 and 35 for"aligomers", each occurrence read oligomers same column 10., line 32 for"nummber" read number column 12, in the table under the heading"Catalyst suspension prepared from" and opposite "Example 40", for"alluminum" read aluminum Signed and sealed this 9th day of February1965 (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A PROCESS FOR THE PRODUCTION OF OLIGOMERS OF 1,3DIENES WHICHCOMPRISES ADDING A 1,3-DIENE TO A CATALYST SYSTEM FORMED BY MIXING (A) ACOMPOUND SELECTED FROM THE CLASS CONSISTING OF IRON (III) HALIDES,TITANIUM (IV) ACID ESTERS, TITANIUM TRIHALIDES, TITANIUM TETRAHALIDES,TITANIUM ESTER HALIDES AND ORGANO-TITANIUM HALIDES; AND (B) METALLICALUMINUM.
 9. A PROCES FOR THE PRODUCTION OF OLIGOMERS OF 1,3DIENE WHICHCOMPRISES ADDING A 1,3-DIENE TO A CATALYSST SYSTEM FORMED BY MIXING (A)A COMPOUND SELECTED FROM THE CLASS CONSISTING OF IRON (III) HALIDES,TITANIUM (IV) ACID ESTERS, TITANIUM TRIHALIDES, TITANIUM TETRAHALIDES,TITANIUM ESTER HALIDES AND ORGANO-TITANIUM HALIDES; (B) AT LEAST ONEMETAL SELECTED FROM THE CLASS CONSISTING OF METALS OF GROUPS IA, IIA,IIB, IIIA, IIIB, IVA, IVB, VB AND VIIB OF THE PERIODIC SYSTEM OF THEELEMENTS; AND (C) AT LEAST ONE HALIDE OF AN ELEMENT SELECTED FROM THECLASS CONSISTING OF THE ELEMENTS OF GROUPS IIB, IIIA, IVA AND VA OF THEPERIODIC SYSTEM OF THE ELEMENTS; AT LEAST ONE OF THE COMPONENTS (B) AND(C) BEING SELECTED FROM THE CLASS CONSISTING OF METALLIC ALUMINUM ANDALUMINUM HALIDE.